Anthraquinone dyes.



lle it known thatwe, CARL .UNITED STATES PATENT: OFFICE.

cam. MULLER. F L nWIGsH'ArEn-on-rnnnnmn Ann MAX HENRY ISL-ER, 0F'MANNHEIM'. GERMANY. Assr NoR-s TO nemsonn ANILIN & SODA FABRIK, orLUDWIGSHAFEN-ON-THE-RHINE, GERMANY. ,A CORPORATION.

ANTHRAQUI ONE DYES.

No Drawing.

l To all whom if m (1 concern:

Mt'ninnn and Max HENRY ISLER, respectively a subject of the King ofBavaria and a citizen ofthe Swiss Republic, residing, respectively; atLndwigshafen on the Rhine and Mannheim, Germany, have invented newandnsein which R- -R may each be equal to hydrogen, allryl, or ai'yl,including anthra,

' quinonyl, and A and A, are either similar or different anthraquinonylresidues. tlhey' represent'yaluable coloring matters. The new amidinscontaining two Z-a'm-ino-anthraquinone residues can be obtained byconvet-ting 'Q-amino-rinthraquinone bodies into their amidins by theapplication of processes known in connection with the production ofamidins of other series, such for instance as those referred to inBernthsens O-rg aniscke Chem/i0, 10th edition, page 199. For instance,beta amino anthra qninone bodiescan be combined with suitable acidderivatives of carboxylic acids, or

t ofortho-carboxylic acids, such for instance as ortho-carboxylic acidesters,amido-et hers, :nnid-chlorids, chlorids, and the'like. New:nnidins, according to the present invention can also be obtained bytreating .EZ-amino-fv anthraquinones with carbon tetrachlorid andnaphthalene, or diphenyl, or other hydrocarbon whichis capable ofcondensing With carbon tetrachlorid while splitting 05112110 gen hydrid.

Our new compounds are characterized by j yielding from yellow to redsolutions in con p examples. ful Improvements in Anthr'aqumone Dyes,

chlor'ic acid being'evolvcd.

centrated si rfuric acid, from yellow to red Specification of LettersPatent. Patented fllay 27, 1913,

. Application filed April 20, 1912. Serial No. 692,133.

they dye cotton from vats yellow to orangeyellow shades. I

The following are examples of how our invention can be carried intopractical effect,- bnt the inventionis not confined to these The partsare by weight: Example" 1: Melt together 10 parts of 2-amino-antln-aquinone, parts of naphthalene and 0.5 part of finelydivided copper. Stir the mixture and heat it in a vessel provided withan inverted condenser at about from 100 to 120 C. Vhen the melt isuniform and well mixed, add 10 parts of carbon tct rachlorid through thecondenser.

Raise the temperature gradually to from- 140 to 150 (1., whereupon thereaction takes plac.e.-'a considerable aniountof hydro- Continuestirring the mass at this temperature untilan increase in the formationofcoloring matter is no longer observable and then allowthetemperature]ofthe mass to fall to about 100 C. and'diliite with oOpa-rtsof toluene. l*ilter, when the temperature of the mass has sunk to from50 to (1, and Wash [rats in alkaline hydrosulfite solution, and

with toluene toreinove-the excess of naph;

thalene. and then wash with alcohol and dry the condensation product. Itcan "re-crystallized from ntho-dichlor-benzene and its melting point isapproximatelyfrom 298 to ,302 C. It is insoluble in water, dilute acidsand alltalis. It (llSSOlVQS fimcon- 'centratcd sulfuric acid, thesolution being It very readily yields a vat jv'ellow-red. upon treatmentwith alkaline hydrosul-fit-e solution, such vat dyeing wool and cot-tonclear yellow shades. .-lilxa1nple 2: Heat together, for a -few hou-rs,.in a vessel provided with ,aninverted condenser, 10 parts ofQ-amino-anthraquinone, 25 parts of diphenyl, 10 parts of carbontetrachlorid, and 0.5 part of finely divided copper, keeping thetemperature between 140 and 160 C. Dilute-the melt with toluene,collectv the condensation prod:- uct, wash first with toluene and thenwith he obtained in a pure ings on cotton and wool.

, On heating this intermediate product with- The products of both of theforegoing exainples can, if desired, be sulfonatedl. The sn-lt'oacidswill dvc wool'yellow shades.

Example 3: )issolve 1 part of orthoformic acid-cthylester HC/(OC H in 5parts of nitrolwnzene and add, gradually, .1 part 'ofQ-amino-anthraquinone, while stirstirring for from 3 to 5 hours at thistemperature and thenprecipitate the intermediate product by ligroin.

'The said product is insoluble in dilute acids and alkalis. yields ayellow solution inconcentrated sulfuric acid and is soluble in alkalinehydrosulfite, but does not dye-cotton from such solution.

' Q-amino-anthraquinone, in the presence of "yellowish red, in whichcolor the ad shades of excellent fastness an indifferent solvent of highboiling point, a vat coloring matter IS obtained which ao- Icording to,analysis and molecular Weight determination, possesses a constitutioncorrespending to the formula: 0

to acids and alkalis and I It is insoluble 1n dilu very ditlicultlysoluble in most organic sol- It: dissolves in conthe solution beingdition of oric acid makes no change- From an orange-red vat it dyescotton orange-yellow against 'the tion of'light, chlorin, and soap.

If the intermediate product. be condensed with l-meth a mixeda-midin isobtained which. dyes Other vents, even on boiling. centrated sulfuricacid may be employed in a similar manner.

Example'at. In order to obtain the amidin derivative directly, allow asolution of 0.23 of a part of ortho forinhz-acid-ethylester in 0.5 partof nitrobenzene to flow, drop by drop, into a boiling mixture of-l partof 2- amino-anthraquiaione and 2 ,parts 'of nitrobenzene. hen thecondensation productlamino-tS-aininomnthraquinone,

I has finished separating out, cool the melt to' i about- 100 C. andfilter-oft the product and purify it by recrystallization from nitroibenzene. In'this example, the Q-amino-anthrziquinone can be-replaced bya derivative thereof, such for instance as 2-amino-3- methylanthraquinon'e and methyl-amino-anthraquinone.

Example 5: benzoyl 2 amino anthraquindne and 4.2 parts of phosphoruspentachlorid and carefully heat'the mixture until-a clear liquid acidhas ceased. When the mixture is cold, add ligroin, filter off theimid-chlorid which is'produced and which possesses a constitutioncorresponding to the formula A-N=CClC H and wash it several times withligroin in order to free it' from phosphorus ony-ch'lorid. crudeimid-chlorid thus obtained with 4.4

of nitrobenzene, and boil the. whole for about 10 minutes whereby atfirst hydrochloric acid is evolved. 'Tlien allow the melt to cool and, bv the addition of alcohol. precipitate the beta-beta-dianthraquinonyl-benzamidin, and filter it oil and re-crystallize it fromortho-dichlor-benzene, whereby glittering yellow needlesare obtained.These a-re'insoluble in dilute acids and alkalis' and very ditficultlysoluble 'in the usual organic solvents. They yield an 0range-yellowsolution in concentrated sulfuric acid and with alkaline hydrosultite,vatwhich dyes cotton and wool lemon yellow shades. I

Example 6: Boil together, for a few hours, while stirring, at from 150to 160 C;,'10 parts of 2amino-:1nthraquinone, 50 parts of nitrohenzencand 4a? parts of benz'o-trichlorid. When the reaction mixture has cooleddown to product and wash 'it with alcohol,- and recrystallize itfrom"nitrobenzene 01" orthodichlor-benzene. The 'amidin thus obtainedmelts at. from 334 to 337? (l, and analysis points to its possessing aconstitution corresponding to the formula sulfite vat, intense lemonyellow. 1

Now what we claim is I '1. As new articles of manufacture amidinscontaining at least two2- in0-antl1raquinone residues and yieldin yellowto red solutions in concentrated sulfuric acid, from yellow to red vatswith alkaline hydrosul- .fite and dyein'g' cotton, from such a. vat,yellow to'orangeiyellow shades.

2 amino 6- Grind together 6.5 "parts of parts of 2-an1ino-antliraquinoneand 30 parts about 40 C-., filter off the is obtained and the evolutionof hydrochloric I ring, at' from 130 to 140 C. Continuei Then mix" theIt isidentical with the product of example; 5 and dyes cotton, from analkaline hydro-' 2. As anew article of -manufacture the I amidincontaining two 2-a1nino-anthraquincentrated sulfuric acid, an orange-redvat in one residues which can'be'obtained by eoniglkaline hydrosulfiteand dyes cot-ton, from densing ,Q-amino-anthraquinbne with benzm. a vat,yellow shades. v I .-trich1orid injthe presence of nitrobenzene, Intestimony whereof we have hereunto 15 6 which probably. possessesaconstitution cop .set our'han'ds in the presence-0f two sub respondingto the formula .scribing'witnesses;

CARL MULLER.

Cm v MAX HENRY ISLER. 'Witnessesg' I 10 and WhlCh melts at abqut from334 to 337 -Josm n PFEIFFER,

' C., yields'an orange-yellowsolution in con- I ERNEST EHBHARDT.

